CN103619587A - Decorative sheet for three-dimensional molding and method for producing same, and decorative molded article using decorative sheet and method for producing same - Google Patents

Decorative sheet for three-dimensional molding and method for producing same, and decorative molded article using decorative sheet and method for producing same Download PDF

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Publication number
CN103619587A
CN103619587A CN201280020448.9A CN201280020448A CN103619587A CN 103619587 A CN103619587 A CN 103619587A CN 201280020448 A CN201280020448 A CN 201280020448A CN 103619587 A CN103619587 A CN 103619587A
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China
Prior art keywords
cosmetic sheet
film layer
methyl
acrylate
resin
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Granted
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CN201280020448.9A
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Chinese (zh)
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CN103619587B (en
Inventor
高野万里
斋藤信雄
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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Priority claimed from JP2011068804A external-priority patent/JP5673281B2/en
Priority claimed from JP2011068803A external-priority patent/JP5673280B2/en
Application filed by Dai Nippon Printing Co Ltd filed Critical Dai Nippon Printing Co Ltd
Publication of CN103619587A publication Critical patent/CN103619587A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/16—Making multilayered or multicoloured articles
    • B29C45/1671—Making multilayered or multicoloured articles with an insert
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14778—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the article consisting of a material with particular properties, e.g. porous, brittle
    • B29C45/14811—Multilayered articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/10—Forming by pressure difference, e.g. vacuum
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
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    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/10—Removing layers, or parts of layers, mechanically or chemically
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0087—Wear resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/26—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
    • B32B2037/268—Release layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/04—Coating on the layer surface on a particulate layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B2309/08—Dimensions, e.g. volume
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    • B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
    • B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
    • B32B2310/0831—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using UV radiation
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    • B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
    • B32B2310/0875—Treatment by energy or chemical effects by wave energy or particle radiation using particle radiation
    • B32B2310/0887—Treatment by energy or chemical effects by wave energy or particle radiation using particle radiation using electron radiation, e.g. beta-rays
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31507—Of polycarbonate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

Provided is a decorative sheet for three-dimensional molding having, on a base film, at least a metal thin film layer and a surface protective layer in this order. The decorative sheet for three-dimensional molding is characterized in that the surface protective layer is a layer formed from a cured product of an ionizing radiation-curable resin composition containing polycarbonate-(meth)acrylate and/or acrylic silicone-(meth)acrylate. The decorative sheet for three-dimensional molding has excellent moldability and imparts a decorative molded article having a metallic finish with design appeal and excellent scratch resistance.

Description

Three-dimensionally shaped by cosmetic sheet and manufacture method thereof and decorated molded article and the manufacture method thereof of having used this cosmetic sheet
Technical field
The present invention relates to a kind of three-dimensionally shaped by cosmetic sheet and manufacture method thereof and decorated molded article and the manufacture method thereof of having used this cosmetic sheet.Further specifically, relate to a kind of metal-like with design excellence, and decorated molded article three-dimensionally shaped by cosmetic sheet and manufacture method thereof and decorated molded article and the manufacture method thereof of having used this cosmetic sheet of excellent scratch resistance is provided.
Background technology
The plastic products with metal-like design can be used as having the substitute of article of the automobile handle and so on of chrome look, with Metal Phase ratio, due to superiority such as the free degree of shape, stronger corrosion stability, lightweight, cheapnesss, therefore, mainly in automobile industry, be widely used.This class makes synthetic resin surface, particularly have three-dimension curved surface or three-dimensional products formed has in the method for metallic luster, after moulding, carry out plating or covering with paint, but these methods need to be processed the environmental problems such as waste water and solvent vapo(u)r, in addition, also have the problems such as expensive.
Therefore, attempt being in recent years used in combination metallic luster sheet material, by produced by insert molding, be produced on the article shaped (for example,, with reference to patent documentation 1 and 2) that surface has metallic luster.
Yet there is following problem in the synthetic resin with such metallic luster: even be subject to slight damage, its gloss reducing and albefaction are also very obvious.
On the other hand, the decorated molded article of decorating by the superficial layer closed assembly spike at products formed is used in the various uses such as vehicle trim part.The forming method of such decorated molded article comprises, cosmetic sheet is shaped to three-dimensional shape in advance by vacuum forming mold, this formed sheet is inserted to injection mold, the resin injection of flow regime is entered in mould, by resin and the integrated forming process of inlaying of formed sheet; And the cosmetic sheet that makes to be inserted in mould is integrated with the molten resin being injected in chamber, synthetic resin surface is implemented to the injection moulding while decorative method (for example,, with reference to patent documentation 3) of decorating when injection moulding.
Above-mentioned decorated molded article is provided with sealer in order to improve surperficial scratch resistance.Yet, with regard to the manufacturing process of above-mentioned decorated resin molded article, in inlaying forming process, by vacuum forming mould, in advance cosmetic sheet is configured as in the process of three-dimensional (solid) shape, in injection molded while decorative method, during preform cosmetic sheet or during injecting molten resin, along cavity inner peripheral surface, stretch and closely sealed process in, there is following problems.That is, due to the empty effect of Vacuum Pressure or by the pressure of molten resin, the stretching that shear stress produces etc., cosmetic sheet is stretched to according to more than the required minimum flow of mold shape, therefore, the sealer of formed products curved face part produces crack.
For the problems referred to above point; the ionization radial line curable resins such as use uv curing resin have been attempted as sealer; by raising, form the crosslink density of resin of the sealer of cosmetic sheet; the surperficial wearability of decorated molded article and scratch resistance are improved, but in products formed curved face part, produce the such problem of cracking while still there is moulding.
In addition; attempt following method, that is, used the ionization radial line curable resins such as uv curing resin as sealer; at the formation stages of cosmetic sheet, form semi-cured state, make resin and cosmetic sheet integrated and after moulding, make it solidify (with reference to patent documentation 4) completely.Yet the sealer that contains uncured resin composition is easily impaired, be difficult to operation, in addition, exist uncured resin composition to be attached to mould and cause the problem of mold fouling.In order to address this problem a little, adopt the method for diaphragm is set on the sealer of semi-cured state, but manufacture numerous and diversely, and be also the main cause that causes cost to rise.
Therefore, expect a kind of sealer that can have scratch resistance and three-dimensionally shaped property concurrently.
In addition, the known resin combination that contains Merlon (methyl) acrylate (for example, with reference to patent documentation 5 and 6), and there is following example: at produced by insert molding, with use in the inner side color sheet at the back side of the surperficial clear sheet of cosmetic sheet, contain on a small quantity the resin combination (with reference to patent documentation 7) of the polycarbonate-based urethane acrylate oligomer of xanthochromia type.Yet, the example that does not use Merlon (methyl) acrylate in the sealer of cosmetic sheet.
On the other hand, silicon Acrylote ketone resin has and utilizes siloxane bond by the acrylate copolymer chain crosslinked structure forming securely, has the characteristic of against weather, heat resistance, resistance to chemical reagents, resistance to water excellence, is widely used in outer decoration coating.But, in the situation that as sealer, formed epithelium becomes hard and crisp and produces cracking sometimes in order to improve the scratch resistance on synthetic resin surface.In order to prevent this cracking; in the situation that silicon Acrylote ketone resin is used as to sealer; produced by insert molding after vacuum forming is carried out to the curing processing (for example,, with reference to patent documentation 8) such as ultraviolet curing with the synthetic resin after sheet material or injection moulding.
Yet, the products formed after three-dimensional processing is cured to processing more numerous and diverse and less economical, be also difficult for carrying out solidifying and processing uniformly.
Therefore, expect a kind of sealer that can have three-dimensionally shaped property and scratch resistance in the excellent chemical medicine of maintenance silicon Acrylote ketone resin concurrently.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2009-220318 communique
Patent documentation 2: No. 4542667 communique of Japan Patent
Patent documentation 3: Japanese Patent Publication 50-19132 communique
Patent documentation 4: Japanese kokai publication hei 6-134859 communique
Patent documentation 5: Japanese kokai publication hei 3-181517 communique
Patent documentation 6: TOHKEMY 2000-351843 communique
Patent documentation 7: TOHKEMY 2003-145573 communique
Patent documentation 8: Japanese kokai publication hei 6-100799 communique
Summary of the invention
The problem that invention will solve
The present invention completes under such situation, its object is, provide a kind of metal-like with design excellence, and decorated molded article three-dimensionally shaped that can obtain excellent scratch resistance is by cosmetic sheet and manufacture method thereof and use the decorated molded article that this cosmetic sheet obtains and the method for manufacturing this decorated molded article.
For the method for dealing with problems
The inventor etc. concentrate on studies in order to realize described object, and result obtains following opinion.
Inventor finds: following sheet material is suitable for realizing its object during by cosmetic sheet as three-dimensionally shaped; described sheet material has at least successively metal film layer and sealer on basement membrane, and described sealer is the layer that the solidfied material by the ionization radial line hardening resin composition that contains Merlon (methyl) acrylate and/or acrylic acid silicone (methyl) acrylate forms.The present invention completes based on this opinion.
; the invention provides a kind of three-dimensionally shaped by cosmetic sheet; it has at least successively metal film layer and sealer on basement membrane; wherein, this sealer is formed by the solidfied material of the ionization radial line hardening resin composition that contains Merlon (methyl) acrylate and/or acrylic acid silicone (methyl) acrylate.
Invention effect
According to the present invention, a kind of metal-like with design excellence can be provided, and can access three-dimensionally shaped cosmetic sheet and the manufacture method thereof of decorated molded article of scratch resistance excellence and decorated molded article and the manufacture method thereof with this cosmetic sheet.
Accompanying drawing explanation
Fig. 1 means the schematic diagram of the section of three-dimensionally shaped the first embodiment by cosmetic sheet of the present invention;
Fig. 2 means the schematic diagram of the section of three-dimensionally shaped the second embodiment by cosmetic sheet of the present invention;
Fig. 3 means the schematic diagram of the section of the first embodiment that uses the three-dimensionally shaped decorated molded article obtaining by cosmetic sheet of the present invention;
Fig. 4 means the schematic diagram of the section of the second embodiment that uses the three-dimensionally shaped decorated molded article obtaining by cosmetic sheet of the present invention.
Symbol description
1,111 basement membranes
2,112 metal film layers
3,114 sealers
4,115 adhesive linkages
5,116,117 priming coats
6,118 plastic bases
10, the 120 three-dimensionally shaped cosmetic sheet of using
20,130 decorated molded articles
113 transparent film layers
The specific embodiment
First, to of the present invention, three-dimensionally shapedly by cosmetic sheet, describe.
[three-dimensionally shaped by cosmetic sheet]
Of the present invention three-dimensionally shaped (following by cosmetic sheet; sometimes referred to as " cosmetic sheet ") be characterised in that; on basement membrane, have at least successively metal film layer and sealer, this sealer is that the solidfied material by the ionization radial line hardening resin composition that contains Merlon (methyl) acrylate and/or acrylic acid silicone (methyl) acrylate forms.More specifically, of the present invention three-dimensionally shaped with in 1 embodiment of cosmetic sheet, metal film layer and above-mentioned sealer directly contacts also closely sealed or across priming coat and closely sealed (below, being sometimes referred to as " the first embodiment ").Of the present invention three-dimensionally shaped with in other embodiment of cosmetic sheet, between above-mentioned metal film layer and above-mentioned sealer, there is transparent film layer (following, to be sometimes referred to as " the second embodiment ").
(basement membrane)
In cosmetic sheet of the present invention, as the basement membrane consideration vacuum forming adaptability of base material, select, can use typically the resin molding being formed by thermoplastic resin.As this thermoplastic resin, generally speaking use acrylonitrile-butadiene-styrene resin (following, be called " ABS resin "), acrylic resin, polypropylene, the polyolefin resins such as polyethylene, polycarbonate resin, vinyl chloride resin etc., wherein, preferred polyolefm resinoid, polycarbonate resin and ABS resin.
In addition, this basement membrane can be used as monofilm or the multilayer film of the same race or that xenogenesis resin forms of these resins.
The thickness of this basement membrane is selected according to purposes, but is generally 200～800 μ m left and right.Between metal film layer and sealer, have in second embodiment of cosmetic sheet of the present invention of transparent film layer; if the thickness of this basement membrane is more than 200 μ m, the convergent force that can suppress the aftermentioned transparent film layer of its shape after due to vacuum forming deforms.On the other hand, no matter whether there is transparent film layer, as long as the thickness of basement membrane is below 800 μ m, by thickening cosmetic sheet, can suppresses operability and reduce.From above-mentioned viewpoint, consider, in addition, in the situation that considering cost etc., the thickness of basement membrane is preferably 250～600 μ m, more preferably 300～500 μ m.
In order to improve this basement membrane and the adaptation that layer is thereon set, also can to the one or two sides of basement membrane, implement according to expectation the surface treatment physics such as oxidizing process or concavo-convexization method or chemistry.
As above-mentioned oxidizing process, can enumerate such as Corona discharge Treatment, plasma treatment, chromium oxidation processes, flame treatment, hot blast processing, ozone/ultraviolet treatment etc., as concavo-convexization method, can enumerate such as sand-blast, solvent treatment method etc.These surface treatments can, according to the suitable selection of the kind of basement membrane, from the viewpoint of effect and operability etc., can preferably be used Corona discharge Treatment method conventionally.
In addition, also can be embodied in the processing that forms priming coat etc. on this basement membrane, also can be pre-formed for adjusting the decorative pattern under the covering with paint of color and the viewpoint of design.
(metal film layer)
Metal film layer in cosmetic sheet of the present invention is the layer of being located in the first embodiment of the present invention between basement membrane and sealer; in there is the second embodiment of aftermentioned transparent film layer; metal film layer is the layer of being located on the face that is positioned at basement membrane side of hyaline membrane, and cosmetic sheet is provided the highlighted property same with metal surface and gives design.
As the metal that can use in the present invention, in the scope of performance effect of the present invention, be not particularly limited, can enumerate: aluminium, nickel, copper, silver, gold, platinum, one-tin brass, indium, chromium, zinc etc.These metals may be used singly or in combination of two or more.
In these metals, preferably indium, tin, chromium or aluminium, consider from being imbued with the viewpoint of extensibility, particularly preferably tin and indium.In addition, the good material tool of extensibility has the following advantages: even sheet material is being stretched and also can not produce cracking for 3 dimension moulding in the situation that.
Formation method as metal film layer of the present invention, can adopt the whole bag of tricks, can use above-mentioned metal and use the vapour deposition methods such as vacuum vapour deposition, sputtering method, ion plating method.Can process various raw material by these methods, from the viewpoint of obtaining the tunicle of ornamental excellence, be preferred.
In the present invention, particularly vacuum vapour deposition, in low cost, and to being considered by the few aspect of the damage of evaporation body, is preferred.Evaporation condition can be according to melt temperature or the suitable setting of evaporating temperature of the metal using.
In addition, except above-mentioned vapour deposition method, also can use the method that is coated with the slurry that contains above-mentioned metal.
As the thickness of this metal film layer, from the viewpoint of extensibility, in the situation that forming with vapour deposition method, optical concentration O.D value is 0.5～3 left and right preferably, more preferably 0.8～1.5 left and right.On the other hand, the in the situation that of coating sizing-agent, preferably 0.1～30 about μ m, preferably 0.5～20 μ m.
In addition, this metal film layer can be set directly on basement membrane.Or also can make to arrange with the following method: the support membrane that one side is provided with to metal film layer be fitted on basement membrane and make this metal film layer and basement membrane opposed, then, peel off support membrane, thereby this metal film layer be set on basement membrane.
In the first embodiment of the present invention, be characterised in that, the sealer of this metal film layer and following detailed description is closely sealed, at interlayer, does not have and take other resin beds such as transparent film layer that PETG (PET) etc. is representative etc.Thus, can give the more excellent mouldability as three-dimensional decorative sheet.In addition, at this, other resin bed is not got rid of the priming coat of the following left and right thickness of 10 μ m using in order to improve the adaptation of metal film layer and sealer etc.
(sealer)
Sealer in cosmetic sheet of the present invention is the layer that the solidfied material by the ionization radial line hardening resin composition that contains Merlon (methyl) acrylate and/or acrylic acid silicone (methyl) acrylate forms.
Above-mentioned ionization radial line hardening resin composition can further contain multifunctional (methyl) acrylate.
At this, ionization radial line hardening resin composition refers to the composition that contains ionization radial line curable resin.Ionization radial line refers to electromagnetic wave or charged particle is intrafascicular has an ionization radial line that can make molecule aggregation or the crosslinked quanta of energy.Conventionally, use ultraviolet ray (UV) or electron beam (EB) as ionization radial line, in addition, also can use the beam of charged ions such as the electromagnetic waves such as X ray, gamma-rays, α line, ion beam.Ionization radial line curable resin refers to by irradiating above-mentioned ionization radial line and is cross-linked, curing resin.
< Merlon (methyl) acrylate >
In the present invention, as ionization radial line curable resin, use Merlon (methyl) acrylate or acrylic acid silicone (methyl) acrylate or this both.First, Merlon (methyl) acrylate is described.
In the present invention, the record of " (methyl) acrylate " refers to " acrylate or methacrylate ".Other similar record also has same implication.
The Merlon using in the present invention (methyl) acrylate is not particularly limited, so long as there is carbonic acid ester bond at main polymer chain, and endways or side chain there is the material of (methyl) acrylate.From crosslinked, curing viewpoint, consider, (methyl) acrylate preferably have 2 officials can more than.
Above-mentioned Merlon (methyl) acrylate is for example transformed to part or all of the hydroxyl of polycarbonate polyol (methyl) acrylate (acrylate or methacrylate) and obtains.This esterification can be undertaken by common esterification.Such as enumerating: the method or 3 that the method, 2 that 1) makes polycarbonate polyol and acryloyl halide or metering system carboxylic acid halides carry out condensation under alkali exists) makes polycarbonate polyol and acrylic anhydride or methacrylic anhydride carry out condensation under catalyst exists) make polycarbonate polyol and acrylic or methacrylic acid carry out the method etc. of condensation under acid catalyst existence.
Above-mentioned polycarbonate polyol is on main polymer chain, to have carbonic acid ester bond, endways or side chain there are 2 above, preferably 2～50, the more preferably polymer of 3～50 hydroxyls.The representative manufacture method of polycarbonate polyol is for utilizing diol compound (A), polyalcohol more than 3 valencys (B) and becoming the method that the compound (C) of carbonyl composition carries out polycondensation reaction.
Diol compound (A) as raw material can be by general formula HO-R 1-OH represents.Wherein, R 1alkyl for the divalent of carbon number 2～20, can contain ehter bond.Be for example alkylidene, cyclohexylene, the phenylene of straight or branched.
As the concrete example of diol compound, can enumerate: ethylene glycol, 1,2-PD, diethylene glycol, DPG, triethylene glycol, polyethylene glycol, neopentyl glycol, 1, ammediol, 1,4-butanediol, 1,5-PD, 3-methyl isophthalic acid, 5-pentanediol, 1,6-hexylene glycol, 1,8-heptandiol, 1, two (2-hydroxyl-oxethyl) benzene of 3-, Isosorbide-5-Nitrae-bis-(2-hydroxyl-oxethyl) benzene, neopentyl glycol, 1,4-cyclohexanediol, 1,4-CHDM etc.Can use separately these glycol, also can be mixed with two or more.
In addition, as the example of polyalcohols more than 3 valencys (B), can enumerate: the alcohols such as trimethylolpropane, trimethylolethane, pentaerythrite, two (trimethylolpropane), dipentaerythritol, glycerine, D-sorbite.And then, can be also the alcohol that oxirane, expoxy propane or other the epoxyalkane of addition 1～5 equivalent on the hydroxyl of these polyalcohols are formed.These polyalcohols can be used alone, but also also mix together two or more.
Become the compound (C) of carbonyl composition for being selected from the arbitrary compound in carbonic diester, phosgene or their equivalent.As its concrete example, can enumerate: the haloformic acid esters classes such as carbonic diester class, phosgene or methylchloroformate, ethyl chloroformate, the phenyl chloroformates such as dimethyl carbonate, diethyl carbonate, carbonic acid diisopropyl ester, diphenyl carbonate, ethylene carbonate, propylene carbonate etc.These can use separately, or are mixed with two or more.
Polycarbonate polyol synthesizes by above-mentioned diol compound (A), more than 3 valencys polyalcohol (B) and the compound (C) that becomes carbonyl composition are carried out to polycondensation under general condition.For example, the raw materials components mole ratio of diol compound (A) and polyalcohol (B) is preferably the scope of 50:50～99:1, in addition, the hydroxyl that the compound (C) that becomes carbonyl composition preferably has with respect to diol compound and polyalcohol with respect to the raw materials components mole ratio of diol compound (A) and polyalcohol (B) is 0.2～2 equivalent.
The hydroxyl value average out to existing in every 1 molecule with the polycarbonate polyol that produces after above-mentioned charge proportion polycondensation more than 3, is preferably 3～50, and more preferably 3～20.If this scope, is formed and needed (methyl) of number acrylate-based by esterification described later, in addition, can give the flexible of appropriateness to Merlon (methyl) acrylate.In addition, the functional end-group of this polycarbonate polyol is generally OH base, but wherein a part can be also carbonate group.
The manufacture method of polycarbonate polyol described above is for example recorded in Japanese kokai publication sho 64-1726 communique.In addition, this polycarbonate polyol, as recorded in Japanese kokai publication hei 3-181517 communique, also can be manufactured by the ester exchange reaction of PCDL and polyalcohols more than 3 valencys.
The molecular weight of the Merlon using in the present invention (methyl) acrylate can be measured by gpc analysis.By the weight average molecular weight that polystyrene standard converts, be preferably more than 500, more preferably more than 1000, further preferably surpass 2000.The upper limit of the weight average molecular weight of Merlon (methyl) acrylate is not particularly limited, and the viewpoint consideration that can not become too high from controlling viscosity, preferably below 100000, more preferably below 50000.From having the viewpoint of scratch resistance and three-dimensionally shaped property concurrently, consider, more preferably surpass below 2000 and 50000, be particularly preferably 5000～20000.
< multifunctional (methyl) acrylate >
Multifunctional (methyl) acrylate using in the present invention so long as 2 officials can be above (methyl) acrylate, be not particularly limited.But, in the situation that needs improve curability, (methyl) acrylate that preferably 3 officials can be above.At this, 2 officials can refer in molecule, to have 2 ethene unsaturated bonds { (methyl) acryloyl group }.
In addition, multifunctional (methyl) acrylate can be any in oligomer and monomer, but considers from improving the viewpoint of three-dimensionally shaped property, preferably multifunctional (methyl) acrylate oligomer.
As above-mentioned multifunctional (methyl) acrylate oligomer, can enumerate such as carbamate (methyl) acrylate quasi-oligomer, epoxy (methyl) acrylate quasi-oligomer, polyester (methyl) acrylate quasi-oligomer, polyethers (methyl) acrylate quasi-oligomer etc.At this, carbamate (methyl) acrylate quasi-oligomer for example can obtain by urethane oligomer being carried out to esterification with (methyl) acrylic acid, and described urethane oligomer can obtain with reacting of PIC by PPG or PEPA.Epoxy (methyl) acrylate quasi-oligomer for example can obtain by making (methyl) acrylic acid react and carry out esterification with the bisphenol-type epoxy resin of lower molecular weight or the oxirane ring of phenolic resin varnish type epoxy resin.In addition, also can use and this epoxy (methyl) acrylate quasi-oligomer be carried out to epoxy (methyl) acrylate oligomer of the partially modified carboxy-modified type forming with duality carboxylic acid anhydrides.The hydroxyl that has a polyester oligomer of hydroxyl at two ends for example being obtained by the condensation of polybasic carboxylic acid and polyalcohol is carried out to esterification with (methyl) acrylic acid or the hydroxyl of the end of oligomer that polybasic carboxylic acid addition epoxyalkane is obtained carries out esterification with (methyl) acrylic acid, can obtain thus polyester (methyl) acrylate quasi-oligomer.Polyethers (methyl) acrylate quasi-oligomer can obtain by the hydroxyl of PPG is carried out to esterification with (methyl) acrylic acid.
In addition, as other multifunctional (methyl) acrylate oligomer, can enumerate: the side chain at polybutadiene oligomer have polybutadiene (methyl) acrylate quasi-oligomer that (methyl) acrylate-based hydrophobicity is high, main chain have polysiloxanes key polysiloxanes (methyl) acrylate quasi-oligomer, to there is the amino resin of many reactive groups in less molecule, carry out amino resin (methyl) acrylate quasi-oligomer that modification forms etc.
As above-mentioned multifunctional (methyl) acrylate monomer, particularly, can enumerate: ethylene glycol bisthioglycolate (methyl) acrylate, propane diols two (methyl) acrylate, BDO two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, hydroxy new pentane acid neopentyl glycol two (methyl) acrylate, two cyclopenta two (methyl) acrylate, caprolactone modification dicyclopentenyl two (methyl) acrylate, oxirane modified phosphate two (methyl) acrylate, allylation cyclohexyl two (methyl) acrylate, isocyanuric acid ester two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, oxirane modification trimethylolpropane tris (methyl) acrylate, dipentaerythritol three (methyl) acrylate, propionic acid modification dipentaerythritol three (methyl) acrylate, pentaerythrite three (methyl) acrylate, epoxy pronane modification trimethylolpropane tris (methyl) acrylate, three (acryloxy ethyl) isocyanuric acid ester, propionic acid modification dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, oxirane modification dipentaerythritol six (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate etc.
More than multifunctional (methyl) acrylate oligomer and multifunctional (methyl) acrylate monomer of narration can be used singly or in combination of two or more.
In the present invention; the Merlon of stating in the use (methyl) acrylate is as in the situation from radiation-curable resin, preferably by having Merlon (methyl) acrylate: the solidfied material of the above-mentioned ionization radial line hardening resin composition of the mass ratio of multifunctional (methyl) acrylate=98:2～70:30 forms sealer.
When the mass ratio of Merlon (methyl) acrylate and multifunctional (methyl) acrylate is greater than 98:2 (, when the amount of Merlon (methyl) acrylate surpasses 98 quality %), scratch resistance reduces sometimes.On the other hand, the mass ratio of Merlon (methyl) acrylate and multifunctional (methyl) acrylate is less than 70:30 hour (that is, the amount of Merlon (methyl) acrylate lower than 70 quality % time), and three-dimensionally shaped property reduces sometimes.More preferably the mass ratio of Merlon (methyl) acrylate and multifunctional (methyl) acrylate is 95:5～80:20.
< simple function (methyl) acrylate >
In the present invention, in order to reduce viscosity of ionization radial line hardening resin composition etc., when stating in the use multifunctional (methyl) acrylate, in the scope of not damaging object of the present invention, proper combination is used simple function (methyl) acrylate.As simple function (methyl) acrylate, such as enumerating: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) isobornyl acrylate etc.Above-mentioned simple function (methyl) acrylate can be used singly or in combination of two or more.
< acrylic acid silicone (methyl) acrylate >
Then, acrylic acid silicone (methyl) acrylate as ionization radial line curable resin is described.
Acrylic acid silicone (methyl) acrylate using in the present invention is not particularly limited, so long as in 1 molecule, a part for acrylic resin structure is substituted by siloxane bond (Si-O), and has more than 2 (methyl) acryloxy (acryloxy or methacryloxy) as the material of functional group at the side chain of acrylic resin and/or main chain end.
As the example of this acrylic acid silicone (methyl) acrylate, for example, can preferably enumerate and at side chain, there is the structure of the acrylic resin of siloxane bond as disclosed in TOHKEMY 2007-070544 communique.
Acrylic acid silicone (methyl) acrylate using in the present invention can, by for example under the existence of radical polymerization initiator, make polysiloxane macromonomer and (methyl) acrylate monomer carry out free-radical polymerized synthesizing.
As (methyl) acrylate monomer, can enumerate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) glycidyl acrylate etc.These (methyl) acrylate monomers can be used separately a kind or be used in combination two or more.
Polysiloxane macromonomer for example can be synthetic by following operation: using n-BuLi or silanol acid lithium as polymerization initiator, six alkyl cyclotrisiloxane are carried out to active anionic polymerization, then carry out end-blocking with the silane that contains free-radical polymerised unsaturated group.As polysiloxane macromonomer, can preferably use the compound shown in following formula (1).
[Chemical formula 1]
Figure BDA0000402202170000111
At this, in formula (1), R 1the alkyl, preferable methyl or the normal-butyl that represent carbon number 1～4.R 2the organic group that represents 1 valency, preferably-CH=CH 2,-C 6h 4-CH=CH 2,-(CH 2) 3o (CO) CH=CH 2or-(CH 2) 3o (CO) C (CH 3)=CH 2.R 3respectively can be identical or different, represent the alkyl of carbon number 1～6, wherein, the alkyl or phenyl of preferred carbon number 1～4, more preferably methyl.In addition, the numerical value of n is not particularly limited, and for example the number-average molecular weight of polysiloxane macromonomer preferably 1000～30000, and more preferably 1000～20000.
Acrylic acid silicone (methyl) acrylate that uses above-mentioned raw materials to obtain for example has the construction unit shown in following formula (2), (3) and (4).
[Chemical formula 2]
Figure BDA0000402202170000121
In formula (2), (3) and (4), R 1, R 3with the R in formula (1) 1, R 3meaning is identical, R 4represent hydrogen atom or methyl, R 5represent the alkyl that alkyl in above-mentioned (methyl) acrylate monomer or the alkyl in glycidyl or above-mentioned (methyl) acrylate monomer or glycidyl etc. can have functional group, R 6represent to have the organic group of (methyl) acryloxy.
Above-mentioned acrylic acid silicone (methyl) acrylate can be used singly or in combination of two or more.
The molecular weight of above-mentioned acrylic acid silicone (methyl) acrylate can be measured by gpc analysis.By the weight average molecular weight that polystyrene standard converts, be preferably more than 1000, more preferably more than 2000.The upper limit of the weight average molecular weight of acrylic acid silicone (methyl) acrylate is not particularly limited, but the viewpoint consideration that can not become too high from controlling viscosity, preferably below 150000, more preferably below 100000.From having the viewpoint of three-dimensionally shaped property, chemical proofing and scratch resistance concurrently, consider, be particularly preferably 2000～100000.
In addition, between the crosslinking points of acrylic acid silicone (methyl) acrylate, mean molecule quantity is preferably 100～2500.If mean molecule quantity is more than 100 between crosslinking points, from the viewpoint of three-dimensionally shaped property, consider, be preferred, if below 2500, from the viewpoint of chemical proofing and scratch resistance, consider, be preferred.
In the present invention; in the situation of acrylic acid silicone (methyl) acrylate as ionization radial line curable resin of stating in the use, by the mass ratio of this acrylic acid silicone (methyl) acrylate and above-mentioned multifunctional (methyl) acrylate, be preferably acrylic acid silicone (methyl) acrylate: the solidfied material of the ionization radial line hardening resin composition of multifunctional (methyl) acrylate=95:5～50:50 is as sealer.
When the mass ratio of acrylic acid silicone (methyl) acrylate and multifunctional (methyl) acrylate is greater than 95:5 (, when the amount of acrylic acid silicone (methyl) acrylate surpasses 95 quality %), scratch resistance and three-dimensionally shaped property reduce sometimes.On the other hand, when the mass ratio of acrylic acid silicone (methyl) acrylate and multifunctional (methyl) acrylate is less than 50:50 (, the amount of acrylic acid silicone (methyl) acrylate is during lower than 50 quality %), chemical proofing and scratch resistance reduce sometimes.More preferably the mass ratio of acrylic acid silicone (methyl) acrylate and multifunctional (methyl) acrylate is 90:10～75:25.
In the present invention, in order to reduce viscosity of ionization radial line hardening resin composition etc., can in the scope of not damaging object of the present invention together with above-mentioned multifunctional (methyl) acrylate suitable above-mentioned simple function (methyl) acrylate that contains.
In the situation that using ultra-violet solidified resin composition as ionization radial line hardening resin composition, preferably with respect to uv curing resin 100 mass parts, add the photopolymerization initator of 0.1～5 mass parts left and right.Photopolymerization can suitable selection from existing habitual material with initator, is not particularly limited.For example can enumerate: benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin n-butylether, benzoin isobutyl ether, acetophenone, dimethylamino benzoylformaldoxime, 2, 2-dimethoxy-2-phenyl acetophenone, 2, 2-diethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl-propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-2 (hydroxyl-2-propyl group) ketone, benzophenone, to phenyl benzophenone, 4, 4 '-diethylamino benzophenone, dichloro benzophenone, 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 2-amino anthraquinones, 2-methyl thioxanthones, 2-ethyl thioxanthones, CTX, 2, 4-dimethyl thioxanthones, 2, 4-diethyl thioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal etc.
In addition, as sensitising agent, can use such as to mesitylenic acid ester, tertiary amines, thio-alcohol sensitizer etc.
In the present invention, preferably use electronic beam curing resin combination as ionization radial line hardening resin composition.This is because electronic beam curing resin combination can solvent free, from environment and healthy viewpoint, considers, more preferably, and does not need photopolymerization initator, can obtain stable curing characteristics.
In addition, in the ionization radial line hardening resin composition of the sealer in forming the present invention, can coordinate various additives according to the expectation physical property of the curing resin layer obtaining.As this additive, can enumerate such as against weather improver, wearability improving agent, polymerization inhibitor, crosslinking agent, infrared absorbent, antistatic agent, cementability improving agent, levelling agent, thixotropy imparting agent, coupling agent, plasticizer, defoamer, filler, solvent, colouring agent etc.
At this, as against weather improver, can use ultra-violet absorber or light stabilizer.Ultra-violet absorber can be any in mineral-type, organic, and as mineral-type ultra-violet absorber, can preferably use average grain diameter is the titanium dioxide, cerium oxide, acidifying zinc etc. of 5～120nm left and right.In addition, as organic ultra-violet absorber, can enumerate for example benzotriazole, particularly, can enumerate: 3-[3-(BTA-2-yl)-5-tert-butyl-hydroxy phenyl of 2-(2-hydroxy-5-methyl base phenyl) BTA, 2-(2-hydroxyl-3,5-di-tert-pentyl-phenyl) BTA, polyethylene glycol] propionic ester etc.On the other hand, as light stabilizer, can enumerate for example hindered amines, particularly, can enumerate: 2-(3,5-di-tert-butyl-4-hydroxyl benzyl)-2 '-n-butylmalonic acid two (1,2,2,6,6-pentamethyl-4-piperidyl) ester, two (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, four (2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylic acid esters etc.In addition, as ultra-violet absorber and light stabilizer, also can use in molecule reactive ultra-violet absorber and the light stabilizer with polymerizable groups such as (methyl) acryloyl groups.In addition, also can under the degree of not damaging the performance (scratch resistance and three-dimensionally shaped property) as the sealer of polymer of the present invention, carry out copolymerization uses.
As wearability improving agent, for example, for inorganic matter, can enumerate: the particles such as Alpha-alumina, silica, kaolinite, iron oxide, diamond, carborundum.Shape of particle can be enumerated ball, ellipsoid, polyhedron, scale shape etc., is not particularly limited, preferably spherical.For organic matter, can enumerate: the synthetic resin pearls such as crosslinked acrylic resin, polycarbonate resin.Particle diameter is made as 30～200% left and right of thickness conventionally.Wherein, spherical Alpha-alumina is high from hardness, the raising successful of wearability, in addition, becomes more readily available the aspect consideration of spherical particle, particularly preferably.
As polymerization inhibitor, can use such as quinhydrones, 1,4-benzoquinone, hydroquinone monomethyl ether, 1,2,3,-thrihydroxy-benzene, tert-butyl catechol etc., as crosslinking agent, can use such as polyisocyanate compounds, epoxide, metal complex compounds, aziridine cpd, oxazoline compound etc.
As filler, can use such as barium sulfate, talcum, clay, calcium carbonate, aluminium hydroxide etc.
As colouring agent, can use red such as quinacridone, isoindolone is yellow, phthalocyanine blue, phthalocyanine green, titanium oxide, carbon black etc. are known painted with pigment etc.
As infrared absorbent, such as using dithiols metal complex, phthalocyanine-like compound, Diimmonium compound etc.
(transparent film layer)
As the second embodiment of cosmetic sheet of the present invention, in order to improve the scratch resistance of this cosmetic sheet and chemical proofing etc., can above-mentioned metal film layer and sealer between sandwich transparent film layer.
As this transparent film layer, from the viewpoint of above-mentioned effect, to consider, the rete preferably consisting of polyester resin, particularly, can enumerate: PETG rete.
The thickness of this transparent film layer is preferably the scope of 10～80 μ m.If thickness is more than 10 μ m, can give good printing adaptability.In addition, if below 80 μ m, the convergent force after vacuum forming can not become strong.Therefore,, even if improve the tensile modulus of elasticity of basement membrane, also can suppress the distortion of shape.The thickness of this transparent film layer is 20～75 μ m more preferably, more preferably 25～70 μ m.
In the second embodiment of cosmetic sheet of the present invention, compare with transparent film layer, preferably the tensile modulus of elasticity of basement membrane at 25 ℃ is large, more than 1000MPa.If the difference of tensile modulus of elasticity is more than 1000MPa, compare with hyaline membrane, can give higher rigidity to basement membrane.Therefore the shape distortion that, can suppress after vacuum forming, transparent film layer contraction causes.From above viewpoint, consider, the tensile modulus of elasticity of further preferred basement membrane at 25 ℃ is than more than the large 1300MPa of the tensile modulus of elasticity of transparent film layer.
On the other hand, the upper limit of the difference of this tensile modulus of elasticity is generally 2000Mpa left and right.If the difference of tensile modulus of elasticity surpasses the upper limit, the tensile modulus of elasticity of basement membrane self becomes too high.Therefore, when producing continuously, be sometimes difficult for adjusting the tension force of extracting out from the basement membrane of reeling condition, be difficult to remove the lax of basement membrane.
In addition, the absolute value of the difference of transparent film layer and the basement membrane linear expansion coefficient under the humidity province of 41～50 ℃ is preferably below 4/10000.If the absolute value of this difference is below 4/10000, after can suppress to fit hyaline membrane and basement membrane or the shape distortion that causes because of the difference of the Shrinkage behavior of hyaline membrane and basement membrane when cooling of the cosmetic sheet after vacuum forming.The absolute value of above-mentioned difference is more preferably below 1/10000, and the absolute value that it is desirable to above-mentioned difference is zero.
In order to improve the adaptation etc. with the layer joining, transparent film layer can be implemented so-called easy bonding processing to one or two sides.
(the three-dimensionally shaped formation by cosmetic sheet)
Then, use Fig. 1 and Fig. 2 to describe the three-dimensionally shaped formation by cosmetic sheet of the present invention.
Fig. 1 means the generalized section of three-dimensionally shaped the first embodiment by cosmetic sheet of the present invention.In the first embodiment, the three-dimensionally shaped structure that is provided with successively metal film layer 2 and sealer 3 on basement membrane 1 that has by cosmetic sheet 10 of the present invention, metal film layer 2 and sealer 3 directly contact and are closely sealed or carry out closely sealed across priming coat.In Fig. 1, illustrate across priming coat 5 and carry out closely sealed situation.In addition, priming coat 5 is that the situation that the adaptation between metal film layer 2 and sealer 3 is lower is inferior, the layer arranging as required.
In addition, preferably between basement membrane 1 and metal film layer 2, there is the adhesive linkage 4 that contains acrylic resin and/or vinyl chloride vinyl acetate copolymer.
Basement membrane 1 in above-mentioned formation, metal film layer 2 and sealer 3 are as mentioned before.
Fig. 2 means of the present invention three-dimensionally shaped by the generalized section in the second embodiment of cosmetic sheet.Cosmetic sheet 120 has the structure that is provided with successively metal film layer 112, transparent film layer 113 and sealer 114 on basement membrane 111.In addition, preferably between basement membrane 111 and metal film layer 112, there is the adhesive linkage 115 that contains acrylic resin and/or vinyl chloride vinyl acetate copolymer.And then, preferably between transparent film layer 113 and sealer 114, there is priming coat 117.In addition, can between metal film layer 112 and transparent film layer 113, be provided with priming coat 116.
Basement membrane 111 in the second embodiment, metal film layer 112, transparent film layer 113 and sealer 114 are as mentioned before.
(being formed on the adhesive linkage between metal film layer and basement membrane)
Of the present invention three-dimensionally shaped with the adhesive linkage 4 or 115 in cosmetic sheet for improving cementability between basement membrane 1 and metal film layer 2 or the cementability between basement membrane 111 and metal film layer 112.As long as just form and be not particularly limited by the resin that can improve cementability.For example, can be the adhesive linkage that is suitable for dry lamination, can be also the adhesive linkage that is suitable for heat bonding (heat-sealing).
Adhesive linkage 4 or 115 thickness are generally 0.5～20 μ m left and right, are preferably 1～5 μ m.
In addition, for example, in the first embodiment shown in Fig. 1, if the adhesive linkage of individual layer 4 cannot obtain, in the situation of the closing force that requires, can carrying out multiple stratification.For example, adhesive linkage is made to these 2 layers of the adhesive linkage 4A (diagram) being formed by resin easy and that metal film layer 2 is closely sealed, the adhesive linkage 4B (without diagram) being made by resin easy and that basement membrane 1 is closely sealed, can obtain stronger closing force.
In addition, even in the situation that carrying out multiple stratification, the thickness of adhesive linkage 4 integral body also as mentioned above, is generally 0.5～20 μ m left and right, is preferably 1～5 μ m.
As the concrete example that forms the resin of adhesive linkage 4 or 115, can enumerate: acrylic resin; Mylar; Cellulosic resin; Vinyl chloride resin, vinyl acetate resin or vinyl chloride/vinyl acetate copolymer resin (following, these are generically and collectively referred to as to " vinyl-based resin ".) etc.
In adhesive linkage, above-mentioned resin can be used singly or in combination of two or more.In these resins, particularly the vinyl-based resin of low acid number described later and acrylic resin can obtain sufficient cementability, and the transparency is also high, and processing ease, therefore preferably.
In the first embodiment of the present invention, in the situation that adhesive linkage 4 is made as to 2 layers of formation, as be used to form with metal film layer join a side layer (4A) resin, so long as above-mentioned vinyl-based resin, in order to prevent the transparence of the above-mentioned metal film layer 2 that heating by rear operation etc. causes, preferably adjust the resinoid average acid number of vinyl.For example, can enumerate: in the situation that metal film layer 2 is the vacuum evaporation coating of tin, the material that the average acid number of this resin is 1～6mgKOH/g (the vinyl-based resin of low acid number).About this vinyl-based resin, if its average acid number is more than 1mgKOH/g, can obtain the sufficient cementability of metal film layer and basement membrane, injection-molded resin etc., therefore preferably.On the other hand, if average acid number is below 6mgKOH/g, can not make above-mentioned metal film layer generation transparence because of the heating of subsequent handling etc., therefore preferably.From above viewpoint, consider, the resinoid average acid number of this vinyl is 2～5mgKOH/g more preferably.
In the situation that adhesive linkage 4 is made to 2 layers, as the concrete example of the resin of the adhesive linkage with the bonding side of basement membrane (adhesive linkage 4B), from the viewpoint of the adaptation with basement membrane, consider preferred acrylic resins and/or vinyl chloride-vinyl acetate copolymerization resin.
In addition, in first and second embodiment, in the situation that above-mentioned adhesive linkage is 1 layer of formation, if above-mentioned vinyl-based resin, the material that the average acid number that can preferably enumerate this resin is 1～6mgKOH/g (the vinyl-based resin of low acid number).About this vinyl-based resin, acid number as average in it is more than 1mgKOH/g, can obtain the sufficient cementability between metal film layer and basement membrane, injection-molded resin etc., therefore preferably.On the other hand, if below 6mgKOH/g, can not make above-mentioned metal film layer generation transparence.From above viewpoint, consider, the resinoid average acid number of this vinyl is 2～5mgKOH/g more preferably.
Disguised etc. in order to give, also can be in adhesive linkage 4 or 115 mixed colorant.By using with the colouring agent of injecting resin homologous ray as colouring agent, can be so that the border of injecting resin and cosmetic sheet be so not eye-catching, thus improve design.
In addition, although not shown, adhesive linkage 4 or 115 and basement membrane 1 or 111 between dyed layer can be set separately.Dyed layer can or have concealed dyed layer for patterned layer, field printing layer.In addition, if dyed layer is colored as to the color similar with basement membrane,, on the section of decorated molded sheet material, the border of basement membrane and dyed layer can be so unobvious, thereby improve design.As the adhesive for dyed layer, can use the adhesive same with above-mentioned adhesive linkage 4 or 115.
As the colouring agent that can be used for above-mentioned adhesive linkage 4 or 115 and dyed layer, be not particularly limited, can use the inorganic pigments such as carbon black (China ink), iron oxide black, titanium white, stibium trioxide, chrome yellow, titan yellow, iron oxide red, cadmium red, ultramarine, cobalt blue, the organic pigment such as quinacridone is red, isoindolone is yellow, phthalocyanine blue or dyestuff, the metallic pigments that formed by flakey paillon foils such as aluminium, brass, pearly luster (pearl) pigment of being formed by squamous paillon foils such as coated by titanium dioxide mica, basic lead carbonates etc.
(formed priming coat between metal film layer and sealer)
In the first embodiment of the present invention, the priming coat 5 as arranging as required between metal film layer 2 and sealer 3, so long as can improve the priming coat of the adaptation of this interlayer, is not particularly limited.Such as enumerating: acrylic resin, vinyl chloride vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, haloflex etc.Wherein, preferably make acrylic polyol and polyvalent isocyanate compound react, and make it the priming coat that heat cure forms.
As above-mentioned polyvalent isocyanate compound, for example, can use 2,4-toluene di-isocyanate(TDI), eylylene diisocyanate, naphthalene diisocyanate, 4, the aromatic isocyanates such as 4 '-methyl diphenylene diisocyanate; 1,6-hexamethylene diisocyanate, 2,2, aliphatic (or ester ring type) isocyanates such as 4-trimethyl hexamethylene diisocyanate, IPDI, HTDI, hydrogenated diphenyl methane diisocyanate, or also can use the addition product of above-mentioned various isocyanates or polymer, such as the addition product of toluene di-isocyanate(TDI), toluene di-isocyanate(TDI) 3 polymers (trimer) etc.
In addition, the thickness of above-mentioned priming coat 5 is generally 0.5～20 μ m left and right, is preferably 1～5 μ m.
In addition, can adjust color or improve design these priming coat 5 mixed colorants, in addition, also can form decorative pattern according to the viewpoint of design.
In addition, this priming coat 5 sometimes in manufacture process after forming priming coat 5, be temporarily wound into roller shape before forming sealer, in order to prevent caking now, can make it to contain the known anticaking agents such as silica.
(formed priming coat between transparent film layer and sealer)
As the priming coat 117 arranging as required between transparent film layer 113 and sealer 114; so long as can improve the priming coat of the adaptation of this interlayer; be not particularly limited, can enumerate: acrylic resin, vinyl chloride vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, haloflex etc.Wherein, preferably make acrylic polymer polyalcohol and the reaction of polyvalent isocyanate compound, and make it the priming coat that heat cure forms.
As above-mentioned polyvalent isocyanate compound, for example, can use 2,4-toluene di-isocyanate(TDI), eylylene diisocyanate, naphthalene diisocyanate, 4, the aromatic isocyanate of 4 '-methyl diphenylene diisocyanate etc.; 1,6-hexamethylene diisocyanate, 2,2, aliphatic (or ester ring type) isocyanates such as 4-trimethyl hexamethylene diisocyanate, IPDI, HTDI, hydrogenated diphenyl methane diisocyanate, or also can use addition product or the polymer of above-mentioned various isocyanates, such as the addition product of toluene di-isocyanate(TDI), toluene di-isocyanate(TDI) 3 polymers (trimer) etc.
In addition, the thickness of this priming coat is generally 0.5～20 μ m left and right, is preferably 1～5 μ m.
In addition, can adjust color or improve design these priming coat 117 mixed colorants, and then, also can form decorative pattern according to the viewpoint of design.
In addition, in manufacture process, this priming coat 117 after forming priming coat 117, be temporarily wound into roller shape before forming sealer, in order to prevent caking now, can make it to contain the known anticaking agents such as silica sometimes.
Moreover, when forming metal film layer 112, in order to obtain cementability, can between hyaline membrane 113 and metal film layer 112, priming coat 116 be set, particularly in the situation that the method for the slurry that use coating contains metal is effective.Material as forming priming coat 116, is not particularly limited, and can use various resins, but preferably uses the resin same with the resin that forms above-mentioned adhesive linkage.In addition, in manufacture process, this priming coat is wound into roller shape after sometimes forming priming coat, in order to prevent caking now, can make it to contain the known anticaking agents such as silica.
(formation of sealer)
Can be according to set sealer 3 or 114 in formation as described below cosmetic sheet of the present invention.
After the coating fluid that preparation contains above-mentioned ionization radial line hardening resin composition, at the layer joining with sealer, be coated with this coating fluid on for example priming coat 5 or 117, and carry out crosslinking curing.In addition, the viscosity of coating fluid so long as can form the viscosity of uncured resin layer on the surface of priming coat 5 or 117 by coating method described later, is not particularly limited.The mode that is 1～1000 μ m by the thickness of take after solidifying on the surface of priming coat 5 or 117 by intaglio plate be coated with, the known mode such as excellent painting, roller coat, reverse roll coating, comma coating, preferably intaglio plate is coated with the coating fluid of preparation, forms uncured resin layer.
To ionization radial lines such as the uncured resin layer irradiating electron beam as above forming, ultraviolet rays, resin bed is solidified.At this, in the situation that using electron beam as ionization radial line, about its accelerating potential, can be suitable selected according to the thickness of the resin of use and layer, but conventionally preferably with the accelerating potential about 70～300kV, uncured resin layer is solidified.
In addition, illuminated line amount preferably forms the amount that the crosslink density of the resin bed of sealer reaches capacity.Conventionally at 5～300kGy (0.5～30Mrad), preferably selected in the scope of 10～50kGy (1～5Mrad).
And then, as electron beam source, be not particularly limited, such as using the various electron-beam accelerators such as Ke Keluofu-Walton, Ernest Thomas Sinton type, model moral Greif type, resonance transformer type, insulating core transformer type or linear pattern, high-frequency and high-voltage type, high-frequency type.
In addition, in there are the embodiments of the present invention of transparent film layer 113, accelerating potential during electron beam irradiation more high transmission ability more can increase.Therefore,, in the situation that use because electron beam deteriorated raw material occurs as transparent film layer 113, the mode preferably equating in fact with the penetratingdepth of electron beam and the thickness of resin bed is selected accelerating potential.Can suppress unnecessary electron beam irradiation to transparent film layer 113, by the deteriorated Min. that is controlled at of the transparent film layer of excess electrons Shu Yinqi 113.
In the situation that using ultraviolet ray as ionization radial line, the ultraviolet radioactive ray that preferably radiation contains wavelength 190～380nm.As ultraviolet source, be not particularly limited, can use such as high-pressure mercury-vapor lamp, Cooper-Hewitt lamp, metal halide lamp, carbon arc lamp etc.
Then, the three-dimensionally shaped manufacture method by cosmetic sheet of the present invention is described.
[the three-dimensionally shaped manufacture method by cosmetic sheet]
The three-dimensionally shaped method by cosmetic sheet of manufacturing above-mentioned first embodiment of the invention (following, sometimes referred to as " manufacture method of cosmetic sheet ") can be used and on basement membrane, directly stack gradually the method for each layer and any in transfer printing.
In the situation that utilizing transfer printing, comprising: on stripping film, form metal film layer operation, by this metal film layer be transferred in epilamellar operation, peel off epilamellar stripping film operation, peeling off the operation of the stacked ionization radial line cured resin composition layer in the surface after stripping film and making this ionization radial line cured resin composition layer crosslinking curing and form the operation of sealer.In addition, in said method, particularly preferably in priming coat being set on stripping film and the embodiment of metal film layer being set thereon.Below, take embodiment that priming coat is set at length describes as example.That is, other embodiment of the manufacture method of cosmetic sheet of the present invention has operation that (a) form priming coat on stripping film, operation that (b) forms metal film layer on this priming coat, (c) and this priming coat and metal film layer are transferred in to epilamellar operation, (d) peel off operation of the operation of the stripping film on priming coat, (e) stacked ionization radial line cured resin composition layer on this priming coat and (f) make this ionization radial line cured resin composition layer crosslinking curing and form the operation of sealer.
((a) operation)
In this operation, on the lift-off processing face of stripping film, by making for example acrylic polyol and polyvalent isocyanate compound reaction heat cure form above-mentioned priming coat.
((b) operation)
In this operation, in above-mentioned (a) operation, on formed priming coat, form metal film layer.Particularly, on above-mentioned priming coat, by metals such as evaporation indium, tin, chromium, aluminium such as vapour deposition methods, form metal film layer.In addition, also can on this metal film layer, be provided as the adhesive linkage of adhesive linkage 4 explanations.
((c) operation and (d) operation)
In (c) operation, above-mentioned priming coat and metal film layer are transferred on basement membrane and make metal film layer and basement membrane joins.In addition, in the situation that adhesive linkage being set by (b) operation on metal film layer, above-mentioned priming coat, metal film layer and adhesive linkage being transferred on basement membrane and making adhesive linkage and basement membrane joins.Next, in (d) operation, peel off epilamellar stripping film.
In addition, above-mentioned adhesive linkage can not arrange and set in advance on basement membrane on metal film layer.
((e) operation)
In (e) operation, be formed at stacked ionization radial line cured resin composition layer on epilamellar priming coat.
Above-mentioned ionization radial line hardening resin composition as mentioned before.
((f) operation)
(f), in operation, by irradiating ionization radial line, make formed ionization radial line cured resin composition layer generation crosslinking curing in above-mentioned (e) operation form sealer.
The method that makes above-mentioned ionization radial line cured resin composition layer generation crosslinking curing and form sealer as mentioned before.
As mentioned above, can effectively manufacture produced by insert molding cosmetic sheet of the present invention.
In directly stacked method, first, on basement membrane 1, form adhesive linkage 4.Adhesive linkage 4 as mentioned before.For the preparation of the resin combination that forms adhesive linkage 4, use the known methods such as intaglio plate coating, excellent painting, roller coat, reverse roll coating, comma coating to be coated on basement membrane 1, form adhesive linkage 4.In addition, can before forming adhesive linkage 4, be pre-formed above-mentioned dyed layer.
Then, on this adhesive linkage 4, form metal film layer.The material of formation metal film layer and formation method are as mentioned before.Then, form formed priming coat between above-mentioned metal film layer and sealer, thereby form sealer.
Below, the manufacture method of the second embodiment of cosmetic sheet of the present invention is described.
First, on the hyaline membrane that forms transparent film layer 113, metal film layer 112 is set.About transparent film layer as mentioned before.In addition, this hyaline membrane can carry out easy bonding processing, and easy bonding processing, from the viewpoint of guaranteeing flatness, is not preferably carried out in surface that metal film layer 112 is set.On the other hand, from the viewpoint of the cementability with sealer, contrary face preferably carries out easy bonding processing.
The material of metal film layer 112 and formation method are as mentioned before.
Then, adhesive linkage 115 is set on metal film layer 112 as required.Adhesive linkage 115 as mentioned before.Then, at the opposition side of the adhesive linkage 115 of transparent film layer 113, priming coat 117 is set as required, coating surface protective layer formation resin combination, forms uncured resin layer.As coating process, can use the known methods such as intaglio plate coating, excellent painting, roller coat, reverse roll coating, comma coating.Then, as mentioned above, this uncured resin layer is cured and forms sealer 114.Then, bonding with basement membrane 111 across above-mentioned adhesive linkage 115, obtain the three-dimensionally shaped cosmetic sheet of using of the present invention.
As mentioned above, can effectively manufacture the three-dimensionally shaped cosmetic sheet of using of the present invention.
Then, decorated molded article of the present invention is described.
[decorated molded article]
Decorated molded article of the present invention is characterised in that, has above-mentioned of the present invention three-dimensionally shapedly by cosmetic sheet on plastic base, and presents the state that the basement membrane of this cosmetic sheet contacts substantially with plastics.
According to Fig. 3 and 4 pairs of decorated molded articles of the present invention, describe.Fig. 3 is used for representing the generalized section of the decorated molded article of the present invention that the cosmetic sheet of the first embodiment obtains, the generalized section that Fig. 4 is the decorated molded article of the present invention that represents to use the cosmetic sheet of second embodiment with transparent resin rete and obtain.According to Fig. 3; show decorated molded article 20 and on plastic base 6, have of the present invention three-dimensionally shapedly with cosmetic sheet 10 (priming coat 5 and the sealer 3 that there is successively as required the adhesive linkage 4 that arranges, metal film layer 2 on basement membrane 1, arrange as required), and present the state that the basement membrane 10 of device sheet contacts with plastic base 6.
On the other hand; decorated molded article 130 shown in Fig. 4 has of the present invention three-dimensionally shaped with cosmetic sheet 120 (priming coat 117 and the sealer 114 that have successively as required the adhesive linkage 115 that arranges, metal film layer 112, the priming coat 116 arranging as required, transparent film layer 113 on basement membrane 111, arrange as required) on plastic base 118, and presents the state that the basement membrane 111 of cosmetic sheet 120 contacts with plastic base 118.
Then, the manufacture method of decorated molded article of the present invention is described.
[manufacture method of decorated molded article]
The manufacture method of decorated molded article of the present invention is characterised in that, comprise following operation: the three-dimensionally shaped of the invention described above used in the sealer side facing die of cosmetic sheet, by heater, from this sealer side, heated the three-dimensionally shaped operation by cosmetic sheet; To after heating, three-dimensionally shapedly by cosmetic sheet, in the mode of the mould inside shape of coincideing, carry out preformed closely sealed with mold inside, then carry out the operation of matched moulds; Injecting resin is expelled to operation in mould; After this injecting resin is cooling, the operation of taking out decorated molded article from mould.
The manufacture method of decorated molded article of the present invention contains following operation (1)～(4):
(1) first, by three-dimensionally shaped, with in the sealer side facing die of cosmetic sheet, by heater, from this sealer side, heat the three-dimensionally shaped operation by cosmetic sheet;
(2) this after heating three-dimensionally shapedly carried out to preformed closely sealed with mold inside by cosmetic sheet in the mode of shape in the mould that coincide, then carry out the operation of matched moulds;
(3) injecting resin is expelled to operation in mould and
(4) this injecting resin cooling after, the operation of taking out decorated molded article from mould.
In above-mentioned (1) and (2), heat the three-dimensionally shaped temperature by cosmetic sheet and be generally 160～190 ℃ of left and right.
In above-mentioned operation (3), make injecting resin melting, in chamber, inject and make this three-dimensionally shaped integrated by cosmetic sheet and injecting resin.In the situation that injecting resin is thermoplastic resin, by heating and melting, forming flow regime, in addition, in the situation that injecting resin is heat-curing resin, by uncured fluid composition at room temperature or the suitable thermosetting flow regime that adds, inject and cooling it solidified.Thus, three-dimensionally shaped integrated and fit by cosmetic sheet and formed resin-formed body, become decorated molded article.The heating-up temperature of injecting resin depends on injecting resin, but is generally 180～320 ℃ of left and right.
In addition, as other embodiment of the manufacture method of decorated molded article of the present invention, be characterised in that, comprise following operation: by the above-mentioned of the present invention three-dimensionally shaped vacuum forming operation of three-dimensional shape that is shaped in advance by vacuum forming mold by cosmetic sheet; Unnecessary part is repaired and is obtained the operation of formed sheet, this formed sheet is inserted to injection mold and closes injection mold, by the resin of flow regime to mold-in injection and by resin and the integrated operation of formed sheet.
The difference of the method and preceding method is: have and be equivalent to preformed vacuum forming operation, and have and from vacuum forming mold, take off and unnecessary part is repaired and obtained the operation of formed sheet, be called as so-called produced by insert molding.Heat three-dimensionally shaped same as above by the temperature of cosmetic sheet and the heating-up temperature of injecting resin.
Embodiment
Then, by embodiment, the present invention is described in further detail, but the present invention is not subject to any restriction of these examples.
In addition, according to following main points, the three-dimensionally shaped all characteristics by cosmetic sheet that obtain in each example are evaluated.
The evaluation > of all characteristics of < cosmetic sheet
(1) mouldability
(1-1) mouldability 1: maximum tension multiplying power 130%
Cosmetic sheet is heated to 160 ℃ with infrared heater, makes it softening.Then, use vacuum forming to carry out vacuum forming (maximum tension multiplying power 130%) with mould, be shaped to the interior shape of mould.By after sheet cools, by cosmetic sheet demoulding from mould.Metewand is as described below.
A: follow well 3D shape, shape retention is also good.
B: in a part for 3D shape portion or maximum tension portion, confirm fine film crackle or albefaction, but practical no problem.
C: follow well 3D shape, but produce warpage and distortion.
D: produce film crackle or albefaction in a part for 3D shape portion or maximum tension portion.
(1-2) mouldability 2: maximum tension multiplying power 100%
In the evaluation method of recording at above-mentioned (1-1), maximum tension multiplying power is made as to 100%, in addition, by evaluating with above-mentioned same method.Metewand is as described below.
A: follow well 3D shape, shape retention is also good.
B: in a part for 3D shape portion or maximum tension portion, confirm fine film crackle or albefaction, but practical no problem.
C: confirm slight film crackle or albefaction in a part for 3D shape portion or maximum tension portion.
D: can not follow the shape of mould, find to film crackle and albefaction on sealer.
(2) scratch resistance
To using #0000 steel wool, with the outward appearance of the test film after reciprocal 5 times of load 1.5kgf (14.7N), evaluate.Metewand as mentioned above.
A: not damage.
B: on surface, confirm fine damage, but the crackle of not filming and albefaction.
C: have slight damage on surface.
D: have significant damage on surface.
(3) chemical proofing
(3-1) chemical proofing 1: the patience to ethanol
To each film piece, 10cm * 10cm drips ethanol, confirms at room temperature to place the outward appearance after 1 hour under the state covering with surface plate.Metewand is as described below.
A: there is no cosmetic variation.
B: confirm extremely slight albefaction, swelling on surface, but do not find significant albefaction, swelling, dissolving etc.
C: confirm extremely slight albefaction, swelling, dissolving on surface.
D: have significant albefaction, swelling, dissolving on surface.
(3-2) chemical proofing 2: the patience to insecticide
In the evaluation method of recording at above-mentioned (3-1), coating insecticide 0.05g replaces ethanol, in addition, and by evaluating with above-mentioned same method.Metewand is as described below.
A: there is no cosmetic variation.
B: confirm extremely slight albefaction, swelling on surface, but do not find significant albefaction, swelling, dissolving etc.
C: confirm extremely slight albefaction, swelling, dissolving on surface.
D: have significant albefaction, swelling, dissolving on surface.
The weight average molecular weight of < electronic beam curing resin and number-average molecular weight >
Use eastern Cao (strain) high speed GPC device processed.The post using is eastern Cao (strain) system, trade name " TSKgel α M ", and solvent is used N-methyl-2-pyrrolidines (NMP), at 40 ℃ of column temperatures, flow velocity 0.5cm 3under/min, measure.In addition, the weight average molecular weight in the present invention and number-average molecular weight are the value that polystyrene standard converts.
Mean molecule quantity > between the crosslinking points after < electronic beam curing resin solidification
Using the value obtaining divided by functional group's number by number-average molecular weight obtained above mean molecule quantity as between crosslinking points.
The physical property > of < basement membrane and hyaline membrane
(1) assay method of tensile modulus of elasticity
The cosmetic sheet obtaining in embodiment and comparative example is cut into " shape dumbbell stretches No. 1 " shape of recording in JIS K6251, as sample.The Tensilon universal testing machine that uses (strain) IAndD to manufacture is measured from 80mm, test speed 50mm/min with spacing jig.
(2) assay method of linear expansion coefficient
The strip that the cosmetic sheet obtaining in embodiment and comparative example is cut into width 3mm * length 15mm is as sample.Use thermo-mechanical analysis (TMA) device, be made as spacing jig from 10mm, 10 ℃/min of test speed and measure under the stretch mode of load 3g, obtain the average coefficient of linear expansion at 41～50 ℃.
In addition, as electronic beam curing resin EB1, use 2 officials' energy polycarbonate acrylic esters (weight average molecular weight: 10000) and 6 officials' energy urethane acrylate oligomer (weight average molecular weight: the mixture of mass ratio 80:20 6000), as EB2, use acrylic acid silicone acrylate (weight average molecular weight: 20000, mean molecule quantity between the crosslinking points after solidifying: 200) and 6 officials' energy urethane acrylate oligomer (weight average molecular weight: the mixture of mass ratio 70:30 5000).
Embodiment 1
On top layer, have on the release layer of biaxial tension PET (thickness 25 μ m, arithmetic average roughness Ra:0.01 μ m) of polysiloxane-based release layer and be coated with acrylic acid/ammonia ester block copolymerized resin, form the transparent priming coat 5 of thickness 2 μ m, using this as stripping film.
Then, on this priming coat 5, evaporation tin forms after metal film layer 2, vinyl chloride/the vinyl acetate copolymer resin that is coated with average acid number 5.6 by reverse on this metal film layer arranges thermal adhesive layer (adhesive linkage 4A), be coated with the bonding agent being formed by acrylic resin and vinyl chloride/vinyl acetate copolymer resin (mass ratio 2:8) thereon, form bond layer (adhesive linkage 4B), obtain thus adhesive linkage 4.Make the as above resulting priming coat 5 that is provided with on stripping film, metal film layer 2, and in the sheet material of adhesive linkage 4, adhesive linkage 4 sides contact with the basement membrane consisting of ABS resin 1 of thickness 300 μ m, then, use following hot press, this hot press uses the stainless steel mirror board of arithmetic average roughness Ra0.05 μ m in priming coat side (face side), in basement membrane side (rear side), use arithmetic average roughness Ra4.0 μ m, 10 of nao-and micro reliefs height RzJIS16 μ m and added the stainless die metallic plate of pear-skin texture pattern, and at 150 ℃, the adding of 0.5MPa, depresses and carries out hot pressing in 10 minutes processing.After hot pressing processing, peel off stripping film, priming coat 5, metal film layer 2, adhesive linkage 4 are needed on to basement membrane 1.
Then, with intaglio plate, reverse the ionizing radiation radiation-curable resin of the kind shown in coating the first table-1 having peeled off the mode that the thickness of take after solidifying on the priming coat surface after stripping film is 10 μ m.This uncured resin layer is irradiated to the electron beam of accelerating potential 165kV, illuminated line amount 50kGy (5Mrad), electronic beam curing resin combination is solidified, form sealer, obtain the three-dimensionally shaped cosmetic sheet of using of the present invention.All characteristics of cosmetic sheet are shown in to the first table-1.
Embodiment 2
Electronic beam curing resin combination as forming sealer, is used the material shown in the first table-1, in addition, obtains similarly to Example 1 the three-dimensionally shaped cosmetic sheet of using of the present invention.All characteristics of the cosmetic sheet obtaining are shown in to the first table.
Embodiment 3
Preparation is as PETG (being recited as below " the PET ") film (thickness 25 μ m, the easy bonding processing of one side) of hyaline membrane.Evaporation tin on the face that does not carry out easy bonding processing of this PET film, arranges metal film layer.The optical concentration OD value of the thickness of metal film layer is 0.7～1.4.
Then, on this metal film layer, by reversing rubbing method, be coated with the vinyl chloride/vinyl acetate copolymer resin of average acid number 5.6, thermal adhesive layer (4A is suitable with adhesive linkage) is set, be coated with the bonding agent being formed by acrylic resin and vinyl chloride/vinyl acetate copolymer resin (mass ratio 2:8) thereon, form bond layer (4B is suitable with adhesive linkage), obtain thus adhesive linkage.
Then, on easy the to be bonding treated side of PET film, with reverse rubbing method, be coated with 2 solution curing type polyurethane resins (host is that polyesters, curing agent are hexamethylene diisocyanate), obtain priming coat.The mode that the thickness of take after solidifying on this priming coat is 10 μ m reverses the electronic beam curing resin combination of the kind shown in coating the first table with intaglio plate.This uncured resin layer is irradiated to the electron beam of accelerating potential 165kV, illuminated line amount 50kGy (5Mrad), electronic beam curing resin combination is solidified, form sealer.
Then, across above-mentioned adhesive linkage, be attached at the basement membrane being formed by ABS resin of thickness 300 μ m, obtain the three-dimensionally shaped cosmetic sheet of using.All characteristics of the cosmetic sheet obtaining are shown in to the first table-1.
Embodiment 4
Prepare PETG (following, to be recited as " PET ") film (thickness 25 μ m, the easy bonding processing of one side), as transparent film layer 113.Evaporation tin on the face that does not carry out easy bonding processing of this PET film, arranges metal film layer 112.The optical concentration OD value of the thickness of metal film layer 112 is 0.7～1.4.
Then, on this metal film layer 112, by reversing rubbing method, be coated with the vinyl chloride/vinyl acetate copolymer resin of average acid number 5.6, hot sealing layer is set, be coated with the bonding agent being formed by acrylic resin and vinyl chloride/vinyl acetate copolymer resin (mass ratio 2:8) thereon, as adhesive linkage 115.
Then, on easy the to be bonding treated side of PET film, with reversing rubbing method coating biliquid curable polyurethane resin (host is that polyesters, curing agent are hexamethylene diisocyanate), obtain priming coat 117.The electronic beam curing resin combination of the kind shown in intaglio plate rubbing method coating table 1-1 for the mode that the thickness of take after solidifying on this priming coat 117 is 10 μ m.To this uncured resin layer, irradiate the electron beam of accelerating potential 165kV, illuminated line amount 50kGy (5Mrad), electronic beam curing resin combination is solidified, form sealer 114.
Then, across adhesive linkage 115, be attached at the basement membrane being formed by ABS resin of the thickness 300 μ m with the tensile modulus of elasticity shown in the first table-1 and linear expansion coefficient, obtain having the of the present invention three-dimensionally shaped cosmetic sheet of using of transparent film layer.
All characteristics of the cosmetic sheet obtaining are shown in to the first table-1 in the lump.
Embodiment 5
The kind of the thickness of transparent film layer and basement membrane is replaced with to the material shown in the first table-1, in addition, obtain similarly to Example 4 the three-dimensionally shaped cosmetic sheet of using of the present invention.All characteristics of cosmetic sheet are shown in to 1-1 table in the lump.
Embodiment 6
The kind of electronic beam curing resin combination is replaced with to the material shown in the first table-1, in addition, obtain similarly to Example 4 the three-dimensionally shaped cosmetic sheet of using of the present invention.All characteristics of cosmetic sheet are shown in to the first table-1 in the lump.
Comparative example 1
Electronic beam curing resin combination as forming sealer, is used the material shown in the first table-2, in addition, obtains similarly to Example 3 the three-dimensionally shaped cosmetic sheet of using.All characteristics of this cosmetic sheet are shown in to the first table-2.
Comparative example 2
Do not form sealer, in addition, make similarly to Example 3 the three-dimensionally shaped cosmetic sheet of using.All characteristics of this cosmetic sheet are shown in to the first table-2.
Comparative example 3
The transparent propene sorrel of used thickness 100 μ m replaces clear PET film, in addition, similarly makes the three-dimensionally shaped cosmetic sheet of using with comparative example 2.All characteristics of this cosmetic sheet are shown in to the first table-2.
[table 1]
The first table-1
[table 2]
The first table-2
Figure BDA0000402202170000292
EB1:2 official can polycarbonate acrylic ester (weight average molecular weight: 10000) and 6 officials can urethane acrylate oligomer (weight average molecular weight: mixture 6000) (mass ratio 80:20)
EB2: acrylic acid silicone acrylate (weight average molecular weight: 20000, molecular weight 200 between crosslinking points) and 6 officials can urethane acrylate oligomer (weight average molecular weight: mixture 5000) (mass ratio 70:30)
EB3:6 official can urethane acrylate oligomer (weight average molecular weight: 2000)
Embodiment 7 and 8
Use respectively 2 kinds of cosmetic sheet that obtain in embodiment 1 and 2, each cosmetic sheet is heated at 170 ℃ of heter temperatures, in the mode of shape in the injection molding mould that coincide, carry out moulding, make sealer side and mold inside closely sealed.Mould is used the mould of the shape that hypocraterimorphous depth degree that the square size of 80mm and vertical dimension 10mm, bight are 2R is high.On the other hand, as injecting resin, use ABS resin [Japanese I And L (strain) manufacture, trade name " Kralastic MTH-2 "], it is formed after molten condition at 230 ℃, be injected in chamber.Injecting resin takes out decorated molded article after solidifying from mould, obtains having the decorated molded article of the formation shown in Fig. 3.
Embodiment 9～12
Use respectively 4 kinds of cosmetic sheet that obtain in embodiment 3～6, each cosmetic sheet is heated at 170 ℃ of heter temperatures, in the mode of shape in the injection molding mould that coincide, carry out moulding, make sealer side and mold inside closely sealed.Mould is used the mould of the shape that hypocraterimorphous depth degree that the square size of 80mm and vertical dimension 10mm, bight are 2R is high.On the other hand, as injecting resin, use ABS resin [Japanese I And L (strain) manufacture, trade name " Kralastic MTH-2 "], it is formed after molten condition at 230 ℃, be infused in chamber.In mold temperature, become the moment of 30 ℃, from mould, take out decorated molded article, obtain having 4 kinds of decorated molded articles of the formation shown in Fig. 4.
Industrial applicibility
Of the present invention three-dimensionally shaped with cosmetic sheet may be provided in type excellent, can be used as three-dimensionally shaped use, there is the metal-like of design excellence, and the decorated molded article of excellent scratch resistance.This decorated molded article can be used as the substitute of the article of handle of automobile for example and so on.

Claims (16)

  1. One kind three-dimensionally shaped by cosmetic sheet; it has at least successively metal film layer and sealer on basement membrane; wherein; this sealer is the layer that the solidfied material by ionization radial line hardening resin composition forms, and described ionization radial line hardening resin composition contains Merlon (methyl) acrylate and/or acrylic acid silicone (methyl) acrylate.
  2. 2. according to claim 1 three-dimensionally shaped by cosmetic sheet, wherein, described metal film layer directly contacts with described sealer and is closely sealed or closely sealed across priming coat.
  3. 3. according to claim 1 three-dimensionally shaped by cosmetic sheet, wherein, between described metal film layer and described sealer, there is transparent film layer.
  4. 4. according to claim 3 three-dimensionally shaped by cosmetic sheet, wherein, the tensile modulus of elasticity of described basement membrane at 25 ℃ is than described transparent film layer more than the large 1000MPa of the tensile modulus of elasticity at 25 ℃.
  5. 5. according to the three-dimensionally shaped cosmetic sheet of using described in claim 3 or 4, wherein, the absolute value of the difference of described transparent film layer and the linear expansion coefficient of described basement membrane under the temperature province of 41～50 ℃ is below 4/10000.
  6. 6. according to the three-dimensionally shaped cosmetic sheet of using described in any one in claim 3～5, wherein, between described transparent film layer and described sealer, there is priming coat.
  7. 7. according to the three-dimensionally shaped cosmetic sheet of using described in any one in claim 3～6, wherein, described transparent film layer is polyester resin rete.
  8. 8. according to the three-dimensionally shaped cosmetic sheet of using described in any one in claim 1～7, wherein, described ionization radial line hardening resin composition also contains multifunctional (methyl) acrylate.
  9. 9. according to claim 8 three-dimensionally shaped by cosmetic sheet, wherein, described multifunctional (methyl) acrylate be 3 officials can more than.
  10. 10. according to the three-dimensionally shaped cosmetic sheet of using described in any one in claim 1～9, wherein, described metal film layer is indium, tin, chromium or aluminum film layer.
  11. 11. according to the three-dimensionally shaped cosmetic sheet of using described in any one in claim 1～10, wherein, between described metal film layer and described basement membrane, has adhesive linkage, and described adhesive linkage contains acrylic resin and/or vinyl chloride vinyl acetate copolymer.
  12. 12. 1 kinds of decorated molded articles, its right to use requires in 1～11 three-dimensionally shaped described in any one to obtain by cosmetic sheet.
  13. The manufacture method of 13. 1 kinds of cosmetic sheet, the method comprises:
    On stripping film, form the operation of metal film layer;
    This metal film layer is transferred in to epilamellar operation;
    Peel off the operation of epilamellar stripping film;
    In the operation of having peeled off stacked ionization radial line cured resin composition layer on the surface after basement membrane;
    Make this ionization radial line cured resin composition layer crosslinking curing and form the operation of sealer.
  14. The manufacture method of 14. 1 kinds of cosmetic sheet, the method comprises:
    (a) on stripping film, form the operation of priming coat;
    (b) on this priming coat, form the operation of metal film layer;
    (c) this priming coat and metal film layer are transferred in to epilamellar operation;
    (d) operation of stripping film being peeled off;
    (e) operation of stacked ionization radial line cured resin composition layer on this priming coat; And
    (f) make this ionization radial line cured resin composition layer crosslinking curing and form the operation of sealer.
  15. The manufacture method of 15. 1 kinds of decorated molded articles, the method comprises:
    Make three-dimensionally shaped the using in the sealer side facing die of cosmetic sheet described in any one in claim 1～11, and from this sealer side, heat this three-dimensionally shaped operation by cosmetic sheet by heater;
    This after heating three-dimensionally shapedly carried out to preformed operation closely sealed with mold inside and matched moulds by cosmetic sheet along mould inside shape;
    Injecting resin is injected into the operation in mould;
    After this injecting resin is cooling, from mould, take out the operation of decorated molded article.
  16. The manufacture method of 16. 1 kinds of decorated molded articles, the method comprises:
    By the three-dimensionally shaped vacuum forming operation of three-dimensional shape that is shaped in advance by vacuum forming mold by cosmetic sheet described in any one in claim 1～11;
    Redundance is repaired and obtained the operation of formed sheet;
    This formed sheet is inserted to injection mold and closes injection mold, thereby make resin and the integrated operation of formed sheet to the resin of mold-in injection flow regime.
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